JP6928048B2 - Manufacturing method of carbon material - Google Patents
Manufacturing method of carbon material Download PDFInfo
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- JP6928048B2 JP6928048B2 JP2019174500A JP2019174500A JP6928048B2 JP 6928048 B2 JP6928048 B2 JP 6928048B2 JP 2019174500 A JP2019174500 A JP 2019174500A JP 2019174500 A JP2019174500 A JP 2019174500A JP 6928048 B2 JP6928048 B2 JP 6928048B2
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
Description
本発明は、炭素材料の製造方法に関する。
本願は、２０１５年７月１４日に、日本に出願された特願２０１５−１４０２７７号、に基づき優先権を主張し、その内容をここに援用する。
The present invention relates to a method for producing a carbon material.
The present application claims priority based on Japanese Patent Application No. 2015-140277 filed in Japan on July 14, 2015, the contents of which are incorporated herein by reference.
炭素材料、例えば炭素繊維は優れた機械的強度を有するため、自動車用部材、航空宇宙素材、スポーツ・レジャー用素材、圧力容器等の工業用素材などとして極めて有用であり、需要が拡大している。また、今後はさらに幅広い分野で利用されることが期待されている。
一般に、炭素繊維は、ポリアクリロニトリルなどの前駆体フィラメントを束ねた前駆体繊維を、酸化性雰囲気で満たした耐炎化炉で加熱して耐炎化処理した後、得られた耐炎化繊維（以下、「耐炎化ポリマー」ともいう。）を窒素などの不活性雰囲気で満たした炭素化炉で加熱して炭素化処理することによって得られる（例えば特許文献１）。
Since carbon materials such as carbon fiber have excellent mechanical strength, they are extremely useful as automobile parts, aerospace materials, sports / leisure materials, industrial materials such as pressure vessels, etc., and their demand is expanding. .. In addition, it is expected to be used in a wider range of fields in the future.
Generally, the carbon fiber is obtained after heating a precursor fiber in which a precursor filament such as polyacrylonitrile is bundled in a flame-resistant furnace filled with an oxidizing atmosphere to make it flame-resistant (hereinafter, "flame-resistant fiber"). It is obtained by heating in a carbonization furnace filled with an inert atmosphere such as nitrogen to carry out carbonization treatment (for example, Patent Document 1).
しかしながら、従来の炭素材料の製造方法では、炭素化処理中の耐炎化ポリマーの熱分解量が大きく、炭素原子の脱離も生じるため、炭素化収率が低い。そのため、耐炎化ポリマーを炭素化する炭素材料の製造コストを低減することは困難である。 However, in the conventional method for producing a carbon material, the amount of thermal decomposition of the flame-resistant polymer during the carbonization treatment is large, and carbon atoms are also desorbed, so that the carbonization yield is low. Therefore, it is difficult to reduce the production cost of the carbon material that carbonizes the flame-resistant polymer.
本発明は上記事情に鑑みてなされたもので、炭素化収率を低下させることなく効率的に炭素材料を製造する方法、および前記方法により得られた炭素材料を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for efficiently producing a carbon material without lowering the carbonization yield, and a carbon material obtained by the above method.
本発明は、以下の態様を有する。
［１］ アクリロニトリル系重合体を含む炭素材料前駆体ポリマー組成物を酸化性雰囲気中で２００〜３５０℃に加熱して耐炎化処理し、密度が１．４０ｇ／ｃｍ３以下の耐炎化ポリマーを得る工程と、アセチレンおよびアセチレン誘導体の少なくとも一方からなるガス状物質（Ａ）を含む非酸化性雰囲気中で、前記耐炎化ポリマーを１６００℃以上の温度を除く温度に加熱して炭素化処理する工程とを含む、炭素材料の製造方法。
［２］ アクリロニトリル系重合体を含む炭素材料前駆体ポリマー組成物を酸化性雰囲気中で２００〜３５０℃に加熱して耐炎化処理し、密度が１．４０ｇ／ｃｍ３以下の耐炎化ポリマーを得る工程と、アセチレンおよびアセチレン誘導体の少なくとも一方からなるガス状物質（Ａ）を含む非酸化性雰囲気中で、前記耐炎化ポリマーを１０００℃以下の温度に加熱して炭素化処理する工程とを含む、炭素材料の製造方法。
The present invention has the following aspects.
[1] A carbon material precursor polymer composition containing an acetyllonitrile-based polymer is heated to 200 to 350 ° C. in an oxidizing atmosphere to be flame-resistant to obtain a flame-resistant polymer having a density of 1.40 g / cm 3 or less. A step of heating the flame-resistant polymer to a temperature other than a temperature of 1600 ° C. or higher in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative to perform carbonization treatment. A method for producing a carbon material, including.
[2] A carbon material precursor polymer composition containing an acetyllonitrile-based polymer is heated to 200 to 350 ° C. in an oxidizing atmosphere to be flame-resistant to obtain a flame-resistant polymer having a density of 1.40 g / cm 3 or less. The step includes a step of heating the flame-resistant polymer to a temperature of 1000 ° C. or lower and carbonizing the polymer in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Method of manufacturing carbon material.
本発明によれば、炭素化収率を低下させることなく効率的に炭素材料を製造する方法、および前記方法により得られた炭素材料を提供できる。 According to the present invention, it is possible to provide a method for efficiently producing a carbon material without lowering the carbonization yield, and a carbon material obtained by the above method.
「炭素材料の製造方法」
以下、本発明の炭素材料の製造方法の一実施形態について説明する。
本実施形態の炭素材料の製造方法は、アクリロニトリル系重合体を含む炭素材料前駆体ポリマー組成物を加熱処理して炭素材料を得るものであり、以下に説明する耐炎化工程と、炭素化工程とを含む。
"Manufacturing method of carbon material"
Hereinafter, an embodiment of the method for producing a carbon material of the present invention will be described.
The method for producing a carbon material of the present embodiment is to obtain a carbon material by heat-treating a carbon material precursor polymer composition containing an acrylonitrile-based polymer. including.
＜アクリロニトリル系重合体を含む炭素材料前駆体ポリマー組成物＞
本発明に用いる炭素材料前駆体ポリマー組成物は、アクリロニトリル系重合体を含む。
アクリロニトリル系重合体としては、アクリロニトリルの単独重合体でもよいし、アクリロニトリルおよびアクリロニトリルと共重合可能なビニル系モノマーの共重合体でもよい。アクリロニトリル系重合体を構成する全ての単位の合計（１００質量％）に対して、アクリロニトリル単位の割合は７０質量％以上が好ましく、ビニル系モノマー単位の割合は３０質量％以下が好ましい。さらに好ましくは、アクリロニトリル単位の割合は９０〜９８質量％であり、ビニル系モノマー単位の割合は２〜１０質量％である。
<Carbon material precursor polymer composition containing acrylonitrile-based polymer>
The carbon material precursor polymer composition used in the present invention contains an acrylonitrile-based polymer.
The acrylonitrile-based polymer may be a homopolymer of acrylonitrile or a copolymer of acrylonitrile and a vinyl-based monomer copolymerizable with acrylonitrile. The ratio of the acrylonitrile unit is preferably 70% by mass or more, and the ratio of the vinyl monomer unit is preferably 30% by mass or less with respect to the total (100% by mass) of all the units constituting the acrylonitrile-based polymer. More preferably, the proportion of the acrylonitrile unit is 90 to 98% by mass, and the proportion of the vinyl-based monomer unit is 2 to 10% by mass.
ビニル系モノマーとしては、アクリロニトリルと共重合可能であれば特に限定されないが、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸２−ヒドロキシエチル、アクリル酸ヒドロキシプロピル等のアクリル酸エステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｎ−ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ウラリル、メタクリル酸２−ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、メタクリル酸ジエチルアミノエチル等のメタクリル酸エステル類；アクリル酸、メタクリル酸、イタコン酸、アクリルアミド、Ｎ−メチロールアクリルアミド、ジアセトンアクリルアミド、スチレン、ビニルトルエン、酢酸ビニル、塩化ビニル、塩化ビニリデン、臭化ビニル、臭化ビニリデン、フッ化ビニル、フッ化ビニリデン等の不飽和モノマー類；ｐ−スルホフェニルメタリルエーテル、メタリルスルホン酸、アリルスルホン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、およびこれらのアルカリ金属塩が挙げられる。これらは、１種単独で用いてもよく、２種以上を併用してもよい。 The vinyl-based monomer is not particularly limited as long as it can be copolymerized with acrylonitrile, and is, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate. , Acrylic acid esters such as hydroxypropyl acrylate; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, uralyl methacrylate, 2-hydroxyethyl methacrylate , Hydroxypropyl methacrylate, diethylaminoethyl methacrylate and other methacrylic acids; acrylic acid, methacrylic acid, itaconic acid, acrylamide, N-methylolacrylamide, diacetoneacrylamide, styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride , Unsaturated monomers such as vinyl bromide, vinylidene bromide, vinyl fluoride, vinylidene fluoride; p-sulfophenyl metallic ether, metalryl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methyl Examples include propanesulfonic acid and alkali metal salts thereof. These may be used alone or in combination of two or more.
アクリロニトリル系重合体は、それ自体、溶液重合、懸濁重合、乳化重合など公知の重合方法により得ることができる。重合により得られたアクリロニトリル系重合体からは、未反応モノマーなどの不純物を除く処理をすることが望ましい。 The acrylonitrile-based polymer itself can be obtained by a known polymerization method such as solution polymerization, suspension polymerization, or emulsion polymerization. It is desirable to remove impurities such as unreacted monomers from the acrylonitrile-based polymer obtained by the polymerization.
炭素材料前駆体ポリマー組成物は、アクリロニトリル系重合体のみからなっていてもよいし、アクリロニトリル系重合体以外の成分（以下、「他の成分」ともいう。）を含んでいてもよい。
他の成分としては、例えばカーボンブラック、カーボンナノチューブ、フラーレン等の他の炭素材料、コロイダルシリカ、ガラス繊維等のガラス材料などが挙げられる。
炭素材料前駆体ポリマー組成物の総質量に対して、アクリロニトリル系重合体の割合は７０〜１００質量％が好ましく、他の成分の割合は０〜３０質量％が好ましい。
The carbon material precursor polymer composition may consist of only an acrylonitrile-based polymer, or may contain components other than the acrylonitrile-based polymer (hereinafter, also referred to as “other components”).
Examples of other components include other carbon materials such as carbon black, carbon nanotubes, and fullerenes, and glass materials such as colloidal silica and glass fiber.
The ratio of the acrylonitrile-based polymer is preferably 70 to 100% by mass, and the ratio of other components is preferably 0 to 30% by mass with respect to the total mass of the carbon material precursor polymer composition.
炭素材料前駆体ポリマー組成物を繊維（以下、「前駆体繊維」ともいう。）として用いる場合、前駆体繊維は、アクリロニトリル系重合体を含む紡糸原液を紡糸して得られる。
紡糸原液に用いられる溶剤としては特に限定されないが、例えばジメチルアセトアミド、ジメチルスルホキシド、ジメチルホルムアミド等の有機溶剤；塩化亜鉛、チオシアン酸ナトリウム等の無機化合物の水溶液などが挙げられる。紡糸して得られる繊維中に金属が混入されにくく、また、工程が簡略化される点で、有機溶剤が好ましい。
紡糸原液中のアクリロニトリル系重合体の濃度は、紡糸工程上、その重合度にもよるが、紡糸原液の総質量に対して、１７質量％以上が好ましく、１９質量％以上がより好ましく、２５質量％以下が好ましい。
When the carbon material precursor polymer composition is used as a fiber (hereinafter, also referred to as “precursor fiber”), the precursor fiber is obtained by spinning a spinning stock solution containing an acrylonitrile-based polymer.
The solvent used in the undiluted spinning solution is not particularly limited, and examples thereof include organic solvents such as dimethylacetamide, dimethyl sulfoxide, and dimethylformamide; and aqueous solutions of inorganic compounds such as zinc chloride and sodium thiocyanate. Organic solvents are preferable because metals are less likely to be mixed into the fibers obtained by spinning and the process is simplified.
The concentration of the acrylonitrile-based polymer in the spinning stock solution is preferably 17% by mass or more, more preferably 19% by mass or more, and more preferably 25% by mass, based on the total mass of the spinning stock solution, although it depends on the degree of polymerization in the spinning process. % Or less is preferable.
紡糸原液を紡糸する方法としては特に限定されないが、湿式紡糸法、乾湿式紡糸法、乾式紡糸法などを適用することができる。
そして、湿式紡糸法、乾湿式紡糸法、乾式紡糸法などで得られた凝固糸を必要に応じて従来公知の水洗、浴延伸、油剤付与、乾燥緻密化、延伸などを施すことにより、所定の繊度を有する前駆体繊維とする。
The method for spinning the undiluted spinning solution is not particularly limited, but a wet spinning method, a dry wet spinning method, a dry spinning method, or the like can be applied.
Then, a predetermined coagulated yarn obtained by a wet spinning method, a dry wet spinning method, a dry spinning method, or the like is subjected to conventionally known water washing, bath stretching, oiling, drying densification, stretching, etc., as necessary. A precursor fiber having a fineness is used.
油剤としては、従来公知のシリコーン系油剤、ケイ素を含まない有機化合物からなる油剤などが挙げられるが、これら以外にも後述する耐炎化工程や炭素化工程での単繊維間の接着を防止できるものであれば、油剤として好適に使用できる。
油剤を付与された繊維は、加熱により乾燥緻密化するのが好ましい。乾燥処理は５０〜２００℃に加熱されたロールに接触させて行うのが効率的である。
また、乾燥された繊維は、引き続き延伸を施すのが好ましい。延伸する方法としては特に限定されないが、乾熱延伸法、熱板延伸法、スチーム延伸法などを適用することができる。
Examples of the oil agent include conventionally known silicone-based oil agents and oil agents composed of organic compounds containing no silicon, but in addition to these, those capable of preventing adhesion between single fibers in the flame resistance step and carbonization step described later. If so, it can be suitably used as an oil agent.
It is preferable that the fibers to which the oil agent is applied are dried and densified by heating. It is efficient to carry out the drying treatment in contact with a roll heated to 50 to 200 ° C.
Further, it is preferable that the dried fibers are continuously stretched. The stretching method is not particularly limited, but a dry heat stretching method, a hot plate stretching method, a steam stretching method, and the like can be applied.
前駆体繊維の単繊維数は２００〜３０００００本が好ましく、１０００〜２０００００本がより好ましく、１２０００〜１０００００本がさらに好ましい。単繊維数が上記範囲内であれば、耐炎化工程および炭素化工程での前駆体繊維の取り扱いが容易であるとともに、得られる炭素材料である炭素繊維を複合材料に成形する際の取り扱いも容易である。 The number of single fibers of the precursor fiber is preferably 200 to 300,000, more preferably 1,000 to 200,000, and even more preferably 12,000 to 100,000. When the number of single fibers is within the above range, it is easy to handle the precursor fibers in the flame resistance step and the carbonization step, and it is also easy to handle when the carbon fiber which is the obtained carbon material is formed into a composite material. Is.
＜耐炎化工程＞
耐炎化工程は、前記炭素材料前駆体ポリマー組成物を酸化性雰囲気中で２００〜３５０℃に加熱して耐炎化処理し、耐炎化ポリマーを得る工程である。
ここで、「酸化性雰囲気」とは、空気雰囲気、もしくは、酸素、二酸化窒素などの公知の酸化性物質を含む雰囲気のことである。これらの中でも、経済性の面から、酸化性雰囲気としては空気雰囲気が好ましい。
<Flame resistance process>
The flame-resistant step is a step of heating the carbon material precursor polymer composition to 200 to 350 ° C. in an oxidizing atmosphere to perform a flame-resistant treatment to obtain a flame-resistant polymer.
Here, the "oxidizing atmosphere" is an air atmosphere or an atmosphere containing known oxidizing substances such as oxygen and nitrogen dioxide. Among these, an air atmosphere is preferable as the oxidizing atmosphere from the viewpoint of economy.
耐炎化処理の温度は２００〜３５０℃である。耐炎化処理の温度が２００℃以上であれば、耐炎化反応速度が遅くなるのを抑制できるので、短時間で耐炎化処理できる。一方、耐炎化処理の温度が３５０℃以下であれば、アクリロニトリル系重合体が熱分解するのを抑制できる。 The temperature of the flameproofing treatment is 200 to 350 ° C. When the temperature of the flame resistance treatment is 200 ° C. or higher, it is possible to suppress the slowdown of the flame resistance reaction rate, so that the flame resistance treatment can be performed in a short time. On the other hand, when the temperature of the flameproofing treatment is 350 ° C. or lower, it is possible to suppress thermal decomposition of the acrylonitrile-based polymer.
炭素材料前駆体ポリマー組成物の耐炎化処理を行う時間は、炭素材料の性能を高める観点から１０分以上が好ましく、１５分以上がより好ましく、２０分以上がさらに好ましい。特に、耐炎化処理を行う時間が２０分以上であれば、耐炎化反応が十分に進行し、斑が生じにくくなり、また、耐炎化工程の後に行われる炭素化工程で炭素材料が分解せずに残存させることができる。耐炎化処理を行う時間は、生産性の観点から、８０分以下が好ましく、６０分以下がより好ましい。 The time for performing the flame resistance treatment of the carbon material precursor polymer composition is preferably 10 minutes or more, more preferably 15 minutes or more, still more preferably 20 minutes or more from the viewpoint of enhancing the performance of the carbon material. In particular, if the flameproofing treatment takes 20 minutes or more, the flameproofing reaction proceeds sufficiently and spots are less likely to occur, and the carbon material does not decompose in the carbonization step performed after the flameproofing step. Can be left in. From the viewpoint of productivity, the time for performing the flameproofing treatment is preferably 80 minutes or less, more preferably 60 minutes or less.
耐炎化処理の方法としては特に限定されず、例えば従来公知の耐炎化炉（熱風循環炉）を用いる方法や加熱固体表面に接触させる方法を採用できる。
炭素材料前駆体ポリマー組成物を繊維（前駆体繊維）として用いる場合、耐炎化炉を用いる方法では、通常、耐炎化炉に入った前駆体繊維を一旦耐炎化炉の外部に出した後、耐炎化炉の外部に配設された折り返しロールによって折り返して耐炎化炉に繰り返し通過させる方法が採られる。
加熱固体表面に接触させる方法では、前駆体繊維を間欠的に加熱固体表面に接触させる方法が採られる。
The method of flameproofing treatment is not particularly limited, and for example, a method using a conventionally known flameproofing furnace (hot air circulation furnace) or a method of contacting with a heated solid surface can be adopted.
When the carbon material precursor polymer composition is used as a fiber (precursor fiber), in the method using a flame-resistant furnace, usually, the precursor fiber that has entered the flame-resistant furnace is once taken out of the flame-resistant furnace and then flame-resistant. A method is adopted in which the fibers are folded back by a folding roll arranged outside the conversion furnace and repeatedly passed through the flameproof furnace.
As a method of contacting the surface of the heated solid, a method of intermittently contacting the precursor fiber with the surface of the heated solid is adopted.
耐炎化工程では、得られる耐炎化ポリマーの密度（ρ）が１．２５〜１．４５ｇ／ｃｍ３になるまで加熱して耐炎化処理することが好ましく、より好ましくは１．２８〜１．４０ｇ／ｃｍ３である。耐炎化ポリマーの密度（ρ）が上記範囲内であれば、後述する炭素化工程での炭素材料の残存量が多くなるため、経済性の面でも有利である。
なお、耐炎化ポリマーの密度（ρ）は、密度勾配管法により測定される値である。
In the flame resistance step, it is preferable to heat the obtained flame resistant polymer until the density (ρ) becomes 1.25 to 1.45 g / cm 3 to perform the flame resistance treatment, and more preferably 1.28 to 1.40 g. / Cm 3 . When the density (ρ) of the flame-resistant polymer is within the above range, the residual amount of the carbon material in the carbonization step described later increases, which is advantageous in terms of economy.
The density (ρ) of the flame-resistant polymer is a value measured by the density gradient tube method.
＜炭素化工程＞
炭素化工程は、アセチレンおよびアセチレン誘導体の少なくとも一方からなるガス状物質（Ａ）を含む非酸化性雰囲気中で、前記耐炎化ポリマーを加熱して炭素化処理する工程である。
<Carbonization process>
The carbonization step is a step of heating and carbonizing the flame-resistant polymer in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative.
ガス状物質（Ａ）は、アセチレンおよびアセチレン誘導体の少なくとも一方からなる。
アセチレン誘導体としては、分子中に炭素原子と炭素原子の間の三重結合を含み、かつ炭素化工程を行う温度で気体である物質であれば特に制限されないが、エチルアセチレン、ｔｅｒｔ−ブチルアセチレンなどが挙げられる。
ガス状物質（Ａ）は、アセチレンの単独ガスでもよいし、アセチレン誘導体の単独ガスでもよいし、アセチレンおよびアセチレン誘導体の混合ガスでもよい。アセチレンおよびアセチレン誘導体の混合ガスの場合、前記混合ガスを構成する全ての分子の合計（１００モル％）に対して、アセチレンの割合は５０モル％以上が好ましく、アセチレン誘導体の割合は５０モル％以下が好ましい。
経済性の観点からは、ガス状物質（Ａ）はアセチレンガスであることが好ましい。
The gaseous substance (A) consists of at least one of acetylene and an acetylene derivative.
The acetylene derivative is not particularly limited as long as it contains a triple bond between carbon atoms in the molecule and is a gas at the temperature at which the carbonization step is performed, but ethyl acetylene, tert-butyl acetylene and the like are not particularly limited. Can be mentioned.
The gaseous substance (A) may be a single gas of acetylene, a single gas of an acetylene derivative, or a mixed gas of acetylene and an acetylene derivative. In the case of a mixed gas of acetylene and an acetylene derivative, the ratio of acetylene is preferably 50 mol% or more, and the ratio of the acetylene derivative is 50 mol% or less with respect to the total (100 mol%) of all the molecules constituting the mixed gas. Is preferable.
From the viewpoint of economy, the gaseous substance (A) is preferably acetylene gas.
ここで、「非酸化性雰囲気」とは、酸素、二酸化窒素などの公知の酸化性物質を実質的に含まない雰囲気のことである。「実質的に」とは、非酸化性雰囲気を形成するガスの全体体積に対して、酸化性物質の体積濃度が１．０体積％以下であることを意味する。
非酸化性雰囲気に含まれるガス状物質（Ａ）の濃度は、１体積％以上が好ましく、２体積％以上がさらに好ましい。
非酸化性雰囲気に含まれるガス状物質（Ａ）以外の成分としては、窒素、アルゴン、ヘリウムなど酸化性を持たない気体（以下、「非酸化性気体」ともいう。）が挙げられる。これらの中でも、経済性の面から窒素であることが好ましい。
Here, the "non-oxidizing atmosphere" is an atmosphere that does not substantially contain known oxidizing substances such as oxygen and nitrogen dioxide. "Substantially" means that the volume concentration of the oxidizing substance is 1.0% by volume or less with respect to the total volume of the gas forming the non-oxidizing atmosphere.
The concentration of the gaseous substance (A) contained in the non-oxidizing atmosphere is preferably 1% by volume or more, more preferably 2% by volume or more.
Examples of the components other than the gaseous substance (A) contained in the non-oxidizing atmosphere include non-oxidizing gases such as nitrogen, argon and helium (hereinafter, also referred to as “non-oxidizing gas”). Among these, nitrogen is preferable from the viewpoint of economy.
炭素化処理の方法としては、例えば炭素化炉にガス状物質（Ａ）と非酸化性気体との混合ガスを導入した状態で、耐炎化ポリマーを導入して保持した後に取り出すことで、耐炎化ポリマーを加熱して炭素化処理する。
炭素化処理の温度としては特に制限されず、得られる炭素材料の使用目的に応じて、通常の炭素化処理の温度範囲で行われる。炭素化処理の温度は一定でもよいし、炭素化処理中に昇温させてもよい。昇温させる場合、例えば炭素化炉内に複数の加熱ゾーンを設置し、上流側の加熱ゾーンから下流側の加熱ゾーンに向かって温度が高くなるように各加熱ゾーンの温度を設定して、上流側の加熱ゾーンから下流側の加熱ゾーンに向かって順次通過させて処理することで実現できる。
As a method of carbonization treatment, for example, in a state where a mixed gas of a gaseous substance (A) and a non-oxidizing gas is introduced into a carbonization furnace, a flame-resistant polymer is introduced, held, and then taken out to make it flame-resistant. The polymer is heated and carbonized.
The temperature of the carbonization treatment is not particularly limited, and the carbonization treatment is carried out within the normal temperature range of the carbonization treatment depending on the intended use of the obtained carbon material. The temperature of the carbonization treatment may be constant, or may be raised during the carbonization treatment. When raising the temperature, for example, multiple heating zones are set in the carbonization furnace, and the temperature of each heating zone is set so that the temperature rises from the upstream heating zone to the downstream heating zone, and the temperature is upstream. This can be achieved by sequentially passing the heat from the heating zone on the side toward the heating zone on the downstream side for processing.
＜その他の工程＞
炭素化工程により得られた炭素材料は、そのまま炭素材料として用いることができるが、必要に応じて公知の方法により黒鉛化したものを炭素材料として用いてもよい。例えば炭素材料を不活性雰囲気中、最高温度が２０００℃を超えて３０００℃以下で加熱することにより黒鉛化された炭素材料が得られる。
<Other processes>
The carbon material obtained by the carbonization step can be used as it is as a carbon material, but if necessary, a material graphitized by a known method may be used as a carbon material. For example, a graphitized carbon material can be obtained by heating the carbon material in an inert atmosphere at a maximum temperature of more than 2000 ° C and 3000 ° C or less.
また、炭素材料を炭素繊維として用いる場合は、炭素繊維に集束性を付与するために、サイジング処理をすることもできる。
サイジング処理に用いるサイジング剤としては、所望の特性を得ることができれば特に限定されないが、例えばエポキシ樹脂、ポリエーテル樹脂、エポキシ変性ポリウレタン樹脂、ポリエステル樹脂を主成分としたサイジング剤が挙げられる。サイジング処理の方法としては、公知の方法を用いることができる。
Further, when the carbon material is used as the carbon fiber, a sizing treatment can be performed in order to impart the focusing property to the carbon fiber.
The sizing agent used in the sizing treatment is not particularly limited as long as desired properties can be obtained, and examples thereof include sizing agents containing an epoxy resin, a polyether resin, an epoxy-modified polyurethane resin, and a polyester resin as main components. As a method of sizing treatment, a known method can be used.
＜作用効果＞
以上説明した、本発明の炭素材料の製造方法によれば、アセチレンおよびアセチレン誘導体の少なくとも一方からなるガス状物質（Ａ）を含む非酸化性雰囲気中で、耐炎化ポリマーを加熱して炭素化処理するので、炭素化収率を低下させることなく効率的に炭素材料を製造することができ、ひいては炭素材料の製造コストを低減できる。炭素化収率の低下を抑制できる理由については、以下のように考えられる。
すなわち、前記ガス状物質（Ａ）を含む非酸化性雰囲気中で耐炎化ポリマーを加熱して炭素化処理すると、アセチレンまたはアセチレン誘導体が接着剤のような役割を果たし、炭素原子の脱離が抑制され、炭素化収率の低下を抑制できると考えられる。また、炭素化処理中に耐炎化ポリマーのポリマー鎖の一部が熱分解して脱離し易い状態になっても、アセチレンまたはアセチレン誘導体の作用により脱離し易い状態になったポリマー鎖が炭素材料に取り込まれることでも、炭素化収率の低下を抑制できると考えられる。
<Effect>
According to the method for producing a carbon material of the present invention described above, the flame-resistant polymer is heated and carbonized in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Therefore, the carbon material can be efficiently produced without lowering the carbonization yield, and the production cost of the carbon material can be reduced. The reason why the decrease in carbonization yield can be suppressed is considered as follows.
That is, when the flame-resistant polymer is heated and carbonized in a non-oxidizing atmosphere containing the gaseous substance (A), acetylene or an acetylene derivative acts like an adhesive and desorption of carbon atoms is suppressed. Therefore, it is considered that the decrease in carbonization yield can be suppressed. Further, even if a part of the polymer chain of the flame-resistant polymer is thermally decomposed and easily detached during the carbonization treatment, the polymer chain that is easily detached by the action of acetylene or an acetylene derivative becomes a carbon material. It is considered that the decrease in carbonization yield can be suppressed by being incorporated.
「炭素材料」
本発明の炭素材料は、上述した本発明の炭素材料の製造方法により得られるものである。
炭素材料を炭素繊維として用いる場合は、マトリックス樹脂と組み合わされて、複合材料として成形され、様々な用途に利用される。
マトリックス樹脂としては特に制限されないが、例えばエポキシ樹脂、フェノール樹脂等の熱硬化性樹脂、アクリル樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂等のラジカル重合系樹脂、熱可塑性アクリル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリカーボネート樹脂、ポリプロピレン樹脂、ポリエチレン樹脂等の熱可塑性樹脂などが挙げられる。また、これらの樹脂の変性体を用いることもできる。また、マトリックス樹脂としては市販品を用いてもよい。
本発明の炭素材料からなる炭素繊維を用いた複合材料の用途としては特に限定されず、例えば、自動車用部材、航空宇宙素材、スポーツ・レジャー用素材、圧力容器等の工業用素材など、幅広い用途に使用できる。
本発明の炭素材料の炭素繊維以外の用途としては、透明導電膜、トランジスタ、キャパシタなどのエレクトロニクス用部材、強化フィラー、導電性フィラーなどのフィラー剤などが挙げられ、本発明の炭素材料は幅広い用途に使用できる。
"Carbon material"
The carbon material of the present invention is obtained by the above-mentioned method for producing a carbon material of the present invention.
When a carbon material is used as a carbon fiber, it is combined with a matrix resin and molded as a composite material, and is used for various purposes.
The matrix resin is not particularly limited, but for example, a thermocurable resin such as an epoxy resin or a phenol resin, a radical polymerization resin such as an acrylic resin, a vinyl ester resin or an unsaturated polyester resin, a thermoplastic acrylic resin, a polyamide resin or a polyimide resin. , Polyplastic resin such as polycarbonate resin, polypropylene resin, polyethylene resin and the like. Further, modified products of these resins can also be used. Moreover, you may use a commercially available product as a matrix resin.
The use of the composite material using carbon fiber made of the carbon material of the present invention is not particularly limited, and is widely used, for example, for automobile members, aerospace materials, sports / leisure materials, industrial materials such as pressure vessels, and the like. Can be used for.
Applications of the carbon material of the present invention other than carbon fibers include electronic members such as transparent conductive films, transistors and capacitors, fillers such as reinforced fillers and conductive fillers, and the carbon materials of the present invention have a wide range of uses. Can be used for.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
「実施例１」
＜炭素材料前駆体ポリマー組成物の繊維の製造＞
アクリロニトリル系重合体（アクリロニトリル単位の含有量：９６質量％、アクリルアミド単位の含有量：３質量％、メタクリル酸単位の含有量：１質量％）を、濃度が２２質量％になるようにジメチルアセトアミド（ＤＭＡＣ）に溶解し、紡糸原液を調製した。この紡糸原液を孔径６０μｍ、孔数２００の紡糸口金を通し、温度３５℃、濃度６７質量％のＤＭＡＣ水溶液を満たした凝固浴中で凝固させ、凝固糸とした。得られた凝固糸を温水中で脱溶媒しながら延伸した後、アミノ変性シリコーン油剤を付与した。さらに加圧スチーム中で延伸して単繊維数２００本、単繊維繊度１．２ｄｔｅｘの炭素材料前駆体ポリマー組成物の繊維（前駆体繊維）を得た。
"Example 1"
<Manufacturing of fibers of carbon material precursor polymer composition>
Dimethylacetamide (content of acrylonitrile unit: 96% by mass, content of acrylamide unit: 3% by mass, content of methacrylic acid unit: 1% by mass) so as to have a concentration of 22% by mass. It was dissolved in DMAC) to prepare a spinning stock solution. This undiluted spinning solution was passed through a spinning spout having a pore size of 60 μm and a number of holes of 200 and coagulated in a coagulation bath filled with a DMAC aqueous solution having a temperature of 35 ° C. and a concentration of 67% by mass to obtain a coagulated yarn. The obtained coagulated yarn was stretched in warm water while removing the solvent, and then an amino-modified silicone oil was applied. Further, the fibers were drawn in pressurized steam to obtain fibers (precursor fibers) of a carbon material precursor polymer composition having 200 single fibers and a single fiber fineness of 1.2 dtex.
＜炭素材料の製造＞
得られた前駆体繊維を空気中、温度２６０℃、緊張下で、加熱時間を２０分として加熱して耐炎化処理し、密度（ρ）が１．３３５ｇ／ｃｍ３の耐炎化ポリマー（耐炎化繊維）を得た（耐炎化工程）。
ついで、熱重量測定装置（株式会社日立ハイテクノロジーズ製、「ＳＴＡ７３００」）に混合ガスの導入経路を設けたものを用い、この装置にガス状物質（Ａ）としてアセチレンガス（東邦アセチレン株式会社製、「原子吸光分析用特殊溶解アセチレン」）と、非酸化性気体として窒素ガス（大陽日酸株式会社製、「高純度窒素ガスＧ２グレード」）とからなる混合ガス（アセチレンガスの体積濃度：２．４体積％、窒素ガスの体積濃度：９７．６体積％）を導入しつつ、耐炎化繊維を加熱した。具体的には、混合ガスを導入した状態で３０℃で５０分保持した後、３０℃から３００℃まで昇温速度５０℃／分で昇温し、さらに３００℃から１０００℃まで１０℃／分で昇温して耐炎化繊維を加熱して炭素化処理し、炭素材料（炭素繊維）を得た（炭素化工程）。雰囲気温度の上昇による繊維の重量変化から炭素化収率を算出した。具体的には、昇温前の耐炎化繊維の重量と各温度での繊維の重量との差を、昇温前の耐炎化繊維の重量で除して炭素化収率を算出した。図１に、温度（横軸）に対して炭素化収率（縦軸）をプロットしたグラフを示す。また、温度１０００℃での炭素化収率を表１に示す。
<Manufacturing of carbon materials>
The obtained precursor fiber was heated in air at a temperature of 260 ° C. under tension for a heating time of 20 minutes to be flame-resistant, and a flame- resistant polymer having a density (ρ) of 1.335 g / cm 3 (flame-resistant). Fiber) was obtained (flame resistance process).
Next, a thermoweight measuring device (manufactured by Hitachi High-Technologies Co., Ltd., "STA7300") provided with a mixed gas introduction path was used, and acetylene gas (manufactured by Toho Acetylene Co., Ltd., manufactured by Toho Acetylene Co., Ltd.) was used as the gaseous substance (A) in this device. A mixed gas (volume concentration of acetylene gas: 2) consisting of "special dissolved acetylene for atomic absorption analysis") and nitrogen gas (manufactured by Taiyo Nisshi Co., Ltd., "high-purity nitrogen gas G2 grade") as a non-oxidizing gas. The flame-resistant fiber was heated while introducing (4.4% by volume, volume concentration of nitrogen gas: 97.6% by volume). Specifically, after holding at 30 ° C. for 50 minutes with the mixed gas introduced, the temperature is raised from 30 ° C. to 300 ° C. at a heating rate of 50 ° C./min, and further from 300 ° C. to 1000 ° C. at 10 ° C./min. The temperature was raised to obtain a carbon material (carbon fiber) by heating the flame-resistant fiber and carbonizing the fiber (carbonization step). The carbonization yield was calculated from the change in fiber weight due to the rise in atmospheric temperature. Specifically, the carbonization yield was calculated by dividing the difference between the weight of the flame-resistant fiber before the temperature rise and the weight of the fiber at each temperature by the weight of the flame-resistant fiber before the temperature rise. FIG. 1 shows a graph in which the carbonization yield (vertical axis) is plotted against the temperature (horizontal axis). Table 1 shows the carbonization yield at a temperature of 1000 ° C.
「比較例１」
混合ガスの代わりに窒素ガスを用いた以外は、実施例１と同様にして炭素繊維を製造した。結果を図１および表１に示す。
"Comparative Example 1"
Carbon fibers were produced in the same manner as in Example 1 except that nitrogen gas was used instead of the mixed gas. The results are shown in FIG. 1 and Table 1.
表１および図１から明らかなように、炭素化処理に際して、アセチレンガスと窒素ガスとからなる混合ガスを用いた実施例１は、窒素ガスのみを用いた比較例１に比べて、炭素化収率が高かった。 As is clear from Table 1 and FIG. 1, in the carbonization treatment, Example 1 using a mixed gas composed of acetylene gas and nitrogen gas has a carbonization yield as compared with Comparative Example 1 using only nitrogen gas. The rate was high.
本発明の炭素材料の製造方法によれば、炭素化収率を低下させることなく効率的に炭素材料を製造できる。 According to the method for producing a carbon material of the present invention, a carbon material can be efficiently produced without lowering the carbonization yield.
Claims (2)
アセチレンおよびアセチレン誘導体の少なくとも一方からなるガス状物質（Ａ）を含む非酸化性雰囲気中で、前記耐炎化ポリマーを１６００℃以上の温度を除く温度に加熱して炭素化処理する工程とを含む、炭素材料の製造方法。 The carbon material precursor polymer composition comprising an acrylonitrile-based polymer is heated to 200 to 350 ° C. in an oxidizing atmosphere and treated flame-resistant, density obtain oxidization polymer 1.28~ 1.40g / cm 3 Process and
In a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative, the flame-resistant polymer is heated to a temperature other than a temperature of 1600 ° C. or higher to carry out carbonization treatment. Method of manufacturing carbon material.
アセチレンおよびアセチレン誘導体の少なくとも一方からなるガス状物質（Ａ）を含む非酸化性雰囲気中で、前記耐炎化ポリマーを１０００℃以下の温度に加熱して炭素化処理する工程とを含む、炭素材料の製造方法。 The carbon material precursor polymer composition comprising an acrylonitrile-based polymer is heated to 200 to 350 ° C. in an oxidizing atmosphere and treated flame-resistant, density obtain oxidization polymer 1.28~ 1.40g / cm 3 Process and
A carbon material comprising a step of heating the flame-resistant polymer to a temperature of 1000 ° C. or lower to perform carbonization treatment in a non-oxidizing atmosphere containing a gaseous substance (A) composed of at least one of acetylene and an acetylene derivative. Production method.
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| US9816207B2 (en) * | 2012-07-12 | 2017-11-14 | Dow Global Technologies Llc | Two-step sulfonation process for the conversion of polymer fibers to carbon fibers |
| US9222201B2 (en) * | 2012-07-12 | 2015-12-29 | Dow Global Technologies Llc | Processes for preparing carbon fibers using sulfur trioxide in a halogenated solvent |
| JP6190673B2 (en) * | 2013-09-06 | 2017-08-30 | 松本油脂製薬株式会社 | Acrylic fiber treatment agent for carbon fiber production and its use |
| JP5963063B2 (en) * | 2014-12-15 | 2016-08-03 | 三菱レイヨン株式会社 | Carbon fiber bundle |
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